Oxyalkylated phenol-aldehyde diols



Patented Mar. 7, 1950 OXYALKYLATED PHENOL-ALDEHYDE DIOLS. ANDDERIVATIVES THEREOF Melvin De Groote, University City, and BernhardKeiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd.,Wilmington, Del., a corporation of Delaware No Drawing. Application May31, 1947, Serial No. 751,629

18 Claims.

This invention relates to new materials or new compositions of matterconsisting of oxyalkylated derivatives of diphenylolmethanes preparedfrom certain phenols and aldehydes, to certain fractionally and totallyesterified forms of such oxyalkylated derivatives, and to methods fortheir preparation. To come Wtihin this invention, a product must havethe required composition and must be surface-active and hydrophile, i.e., it must be water-soluble, water-dispersible, or selfemulsiflable.Products of the kind disclosed and claimed herein are themselves usefulin various arts. In addition, they are useful as intermediates in thepreparation of other products, as will be mentioned below.

Our invention requires first the preparation of diphenylolmethanes fromcertain aldehydes and phenols, in the proportions and under theconditions set out in detail below; and the subsequent oiiyalkylation ofsuch parent compounds by the use of certain oxyalkylating agents toproduce a principal embodiment of our invention. Such oxyalkylatedproducts are contemplated for use in various arts. They are also usefulas intermediates in preparing a second principal embodiment of ourinvention. They are further useful as intermediates in the preparationof certain derivatives not included in the present invention.

The reagents of this invention may be visualized as substitutedmethaues, in which two of the four methane carbon valences are satisfiedby phenolic residues of specified composition; one of the two remainingpositions is occupied by hydrogen; and the last position is occupiedeither by hydrogen or by a hydrocarbon radical, whether of the alkyl,aryl, aralkyl, acyclic, cyclic, or alicyclic type, depending upon thenature of the aldehydic reactant used. The reagents may likewise bereadily visualized as consisting of two modified phenolic residuesconnected by a methylene or a mono-substituted methylene bridge.

In our reagents, the molecule contains two residues derived from certaindi-functional and tri-functional monocyclic and monohydric phenols or amixture thereof; but they are usually derived from di-iunctionalphenols. Di-functional (di-reactive) phenols, to be suitable asreactants here, must contain one hydrocarbon substituent in the 2,4,6position. Such hydrocarbon substituent may contain from 9 to 24 carbonatoms. In the case of the tri-functional phenolic reactants, also, onlythose having hydrocarbon substituents containing 9 to 24 carbon atoms,occupying the 3,5 position, are suitable. In the case of suchtri-functional phenolic reactants,

there is no substituent group or radical to be considered, as to the2,4,6 position, it being occupied by hydrogen.

Phenolic bodies are widely used in reslnlfication processes. In suchreactions, the 2,4, and 6 positions of the phenolic ring (numbering fromthe phenolic hydroxyl group as occupying position 1) are the reactivepositions. Since these three positions are full equivalents in suchreactions, we shall refer to them herein as the 2,4,6 position, meaningthat any one of them is equally intended. (It should be distinctlyunderstood that we do not consider our reagents to be resins, however.)Where all three such positions are occupied by hydrogen, they areobviously all three available in such reactions; and the phenol istermed tri-functional or tri-reactive. We have found that tri-iunctionalphenols are usable as phenolic reactants herein, provided that position3 or position 5 thereof is occupied by hydrocarbon radicals possessingat least 9 carbon atoms and not over 24 carbon atoms.

Mono-functional (mono-reactive) phenols are not included as usablereactants to produce our reagents. See our co-pending application SerialNo. 586,269, filed April 2, 19%, now Patent No. 2,430,003, in thisconnection.

The aldehydic reactant is present for the purpose of supplying theconnecting bridge or link between two molecules of the phenol. Theproportion of aldehydic reactant is carefully controlled, so as toproduce a maximum amount of diphenylolmethane. We have found that if oneuses 1 mole of aldehyde for 2 moles of phenol, i. e., the theoreticalproportions of reactants, the reaction is inclined to be somewhat shortof complete. We have therefore found it advisable to use slightly largerthan theoretical proportions of aldehydic reactant, e. g., 05 orpossibly as much as 1.1-0 moles of aldehyde for 2 moles of phenol. Anappreciably larger proportion of the aldehydic reactant should not beemployed, bi.- cause it is conducive to the formation of moleculescontaining more than 2 phenolic nuclei each; and these are distinctlynot included within the scope of our invention. It appears, however,that some slight excess of aldehyde, of the order stated, is desirable.If a minor proportion. of some product containing 3 phenolic nuclei inthe molecule happened to be formed in the preparation of our reagent,its presence would not be detrimental to such products use in theapplications stated below. Such impure or, rather, technically pureproduct is still to be considered as coming within our invention. Thesame is true (the meta position) it any uncombined excess 01 phenolhappens be present.

Use of an appreciably smaller ratio of aldehyde to phenol than 1 to 2merely results in incomplete combination of the phenol, the amountremaining uncombined contributing little or, nothing to the value of theproduct and at the same time raising its cost. Therefore, reactantproportions should be quite closely adhered to, and should be of theorder of those just recited above.

While we include a limited class of trifunctional phenols within thereactants usable to produce our reagents, we greatly prefer to employthe particular class of (ll-functional phenols noted herein.

Di-Iunctional phenols are'characterized by the presence 01' only twopositions reactiv in resiniflcation processes. In other words, one ofthe three otherwise reactive positions mentioned above is occupied by asubstituent of some character. For example, if the substituent occupiesposition 2 or position 6 (numbering from the hydroxyl group as inposition 1, substitution, .is ortho; and only positions a and 6 or 2 and4.; respectively, are available for participation in reactions of thattype; If position 4 is occupied, substitution is para; and onlypositions 2 and 6 are available. In general, para-substituted phenolsare more readily procurable commercially and command lower prices thanortho isomers.

For these reasons, and also because in some instances we have found thepara isomers to produce superior reagents, we prefer to employ suchpara-substituted phenols as reactants. However, it should be clearlyunderstood that, for the purpose of producing the reagents of thisinvention, the ortho and the para isomers are full equivalents.

Such para di-functional phenols are sometimes prepared from rawmaterials which contain methyl groups in either or both positions 3 andSince such 3,5 position is not afiected by reactions of the kind justdiscussed above, we specifically include (ii-functional phenols preparedfrom meta-cresol or 3,5 xylenol (i. e., di-functional phenols in whicheither or both the 3 and 5 positions are occupied by methyl groups)within the class of raw materials for producing our reagents.

Mixtures of di-iunctional phenols may be employed to produce ourreagents, instead of a single member of the specified class. But not alldi-functional phenols are usable. These same statements apply totri-functional phenols,

To be acceptable for use herein, a di-functional phenol must contain asubstituent in the 2,4,6 position, which substituent is a hydrocarbonradical. Such hydrocarbon radical may contain from 9 to 24 carbon atoms,without departing from our invention. The hydrocarbon radicals may bealkyl, aryl, aralkyl, acyclic, cyclic, or alicyclic. It is sometimesdesirable to produce our reagent from a phenol containin an arylsubstituent, and subsequently, to convert such aryl substituent to acyclic radical by conventional hydrogenation, e. g., so it may be usedwhere aromatic derivatives are potentially hazardous, as in cosmetics.Any such hydrogenation procedure must of course not destroy necessaryfunctional groups in our products, or the intermediates used to producethem, like the phenolic hydroxyl groups or the alcoholic hydroxyl groupsintroduced by oxyalkylation, as described below.

The phenols used as reactants to prepare our reagents are specified to bmonocyclic phenols,,

in the sense that they do not contain a condensed or fused ring. Thenaphthols are specifically excluded from the present application. Ourphenolic reactants may, however, have cyclic substituents containingaromatic or fused aromatic rings, or may contain such aromatic ring aspart of an aralkyl substituent, etc. They are also required tobemonohydric, i. e., they contain only one phenolic hydroxyl group permolecule.

In our products, both phenolic hydroxyl groups present in the parent'dipherwlolmethane, as prepared from a di-functional or tri-functionalphenol and an aldehyde, have been replaced by a residue obtained from analpha-beta low molal alkylene oxide. The alkylene oxides which we mayuse in preparing our reagents are limited to those containing 4 carbonatoms or less. They consist of ethylene oxide, propylene oxide, butylonoxide, glycide, and methylglycide. Glycide may be considered to behydroxypropylene oxide; and methylglycide, hydroxybutylene oxide.

Such alkylene oxides react with various substances, including phenols,to introduce one or more divalent alkyleneoxy groups, i. e.,ethyleneoxy, -C2H4O; propyleneoxy, -C3Ha0;butyleneoxy,--C4HaO-,orgenerally,CnHzO; or, in the case of glycide andmethylglycide, hy-

, droxypropyleneoxy (-C3H5(OH)O) or hydroxybutyleneoxy (-C4H1(OH)O),into the phenol molecule. Such alkylene oxide residue is interposedbetween the phenolic hydroxyl group's oxygen atom and its hydrogen atom.The result of this reaction is to convert the phenolic hydroxyl groupinto a glycol or hydroxylated glycol radical, one alcoholic hydroxylgroup 0! which has been etherified with the phenolic residue, and theother or others are free to participate in any subsequent desiredreactions. Depending upon the proportion of alkylene oxide available andthe conditions under which reaction is conducted, it is possible tointroduce from 1 to as many as 60 or more alkyleneoxy units at eachphenolic hydroxyl group, in this manner. In the present invention, wedesire to specify that from 1 to 60 such units may be present for eachoriginal phenolic hydroxyl group in our reagents, so long as they retaincertain specified properties stated in detail below.

Because glycide and methylglycide are so infrequently employed, we shallconfine our subsequent remarks below essentially to ethlyenc oxide,propylene oxide, and butylene oxide. It must be always remembered thatwhen we speak henceforth of alkylene oxide residues, or illustrate ourstatements by references to one or more of the three non-hydroxylatedmembers of our class, we non the less always include glycide andmethylglycide as full equivalent thereof. When we refer to glycol or.polyglycol radicals herein, it is to be understood that hydroxyglycol orhydroxypolyglycol radicals are meant it the reactant is glycide ormethylglycide. Glycide is so reactive that its use is not recommended,because of the hazard involved. It nevertheless comes within the purviewof our invention. Mixtures of all our alkylene oxide reactants may beused, if desired, instead of any single one 01 them.

In our simpler products, then, the two phenolic hydroxyl groups of adiphenylolmethane have been converted into two glycol or polyglycolradicals having one free alcoholic hydroxyl group (in the case ofglycideand methylglycide-de- 75 rived reagents, two or more) each. Inour more complex reagents, such free alcoholic groups have beenesterified, e. g., with a higher fatty acid, to produce fractional ortotal esters. Detailed consideration of this phase of our invention isdeferred momentarily.

The radical or residue which appears in our reagents as a bridge or linkbetween the two modified phenolic radicals discussed above is obtainedfrom a suitable reactive aldehyde containing not more than 8 carbonatoms. Such aldehyde may be aliphatic; it may be aromatic; or it may becyclic. The simplest aldehydic reactant is formaldehyde; and because ofits wide availability, low cost, and high reactivity in the presentinvention, we name it as our generally preferred reactant of this class.Its cyclic polymer, trioxane, may sometimes be employed to advantage.Its homologues, such as acetaldehyde or its polymer paraldehyde,propionaldehyde, butyraldehyde, and heptaldehyde, are obviousequivalents. Aromatic aldehydes like benzaldehyde are usable.Furfuraldehyde, representative of the class of heterocyclic aldehydes,is usable, etc. Obviously, where a material, although an aldehyde,possesses some more reactive functionality than its aldehydic character,it may not react as an aldehyde'here, and hence may be unsuitable foruse in preparing our reagents. Mixtures of suitable aldehydes containingless than 9 carbon atoms are usable to prepare our reagents.

To summarize the foregoing briefly, our reagents are prepared fromdiphenylolmethancs which have themselves been obtained from low molalaldehydes and certain (ll-functional or trifunctional phenols, but notfrom mono-funetional phenols. If procurable commercially, suchdiphenylolmethanes may be purchased rather than prepared. Suchdiphenylolmethanes are then subjected to oxyalkylation by means of a lowmolal oxyalkylating agent, in which process from 1 to 60 alkyleneoxyresidues are introduced at each phenolic hydroxyl group, between theoxygen and hydrogen atoms thereof. Such oxyalkylated diphenylolmethanesare themselves an important embodiment of our inventions reagents. Theirfractional or total esters, particularly those of high molalmonocarboxylic acids, constitute a second important embodiment of ourreagents.

Our reagents may be illustrated by the following type formulas:

In the first formula, R1 refers to a radical derived from adi-functional phenol in which the hydrocarbon substituent in the 2,4,6position may possess from 9 to 24 carbon atoms, or derived from atri-functional phenol having a 3,5 hydrocarbon substituent possessingfrom 9 to 24 carbon atoms. The two R1 radicals may be the same or theymay be different. Each R1 no longer possesses its original phenolichydroxyl group, the latter having been replaced by residues obtainedfrom alkylene oxide reactants and which possess terminal alcoholichydroxyl groups, in free or esterified form.

6 In other words, the radicals R1 may be further detailed as in thesecond formula shown, where they areseen to consist of the radicals Ro0(R40) nR'l wherein R3 is the phenolic nucleus containing a substituenthydrocarbon radical, as above defined; R4 is an alkylene orhydroxyalkylene radical.

or C4H7(OH); n is a number between 1 and 60: and R7 is either hydrogenor the acyl radical of a high molal or a low molal monocarboxylic acid,with the limitation that if either occurrence of R1 represents an acylradical, at least one such occurrence of R: must represent the acylradical of a high molal monocarboxylic acid, as explained further below.Rs in both formulas may be either hydrogen or an organic radicalcontaining 7 carbon atoms or less; but at least one occurrence mustrepresent hydrogen. (Where both occurrences of R2 represent hydrogen,formaldehyde was the parent aldehyde reactant. Where benzaldehyde wasthe aldehyde employed, the second R2 would represent the CsHs radical.If furfuraldehyde were the aldehyde used, the second occurrence of R2would represent the cyclic radical CiHzO. Ii acetaldehyde were used, thesecond R2 would represent the aliphatic radical, CH3. These examples areillustrative).

To detail this last generic formula still further, so as to show thephenolic residue in clearer fashion, the following formula is oflered:

In this formula, one occurrence of R2 represents hydrogen and the otheroccurrence represents either hydrogen or an organic radical containing'7 carbon atoms, or less, as before. R4 is an allrylene radical orradicals each containing from a to a carbon atoms (and also containing ahydroxyl group if derived from glycide or methylglycide).

" The n occurrences of the alkyleneoxy radical R40 number between 1 and60, for each occurrence oi" 11 shown. R5 is a hydrocarbon radicalcontaining from 9 to 24 carbon atoms and located either in the 2,4,6position of a parent di-functional phe nol or in the 3,5 position of aparent tri-functional. phenol. Re is a monocyclic aromatic ring, whichmay contain a methyl group in either or both the 3 and 5 positions. ifthe phenol was (ii-functional. R1 represents hydrogen or an acyl radicalderived from a monobasic carboxylic acid, with the proviso that ifeither occurrence of R7 represents an acyl radical, at least one suchacyl radical must be that of a high molal monocarboxyllc acid,containing from 8 to 32 carbon atoms.

While the following examples show a number oi representative usablephenols, it may be well to describe our preferred trl-functionalphenolic reactants here. These are prepared from the phenoliccompositions present in or derived from the oils extracted from the,anacardium genus of the anacardiaceae family. Cashew nutshell liquid isdescribed as consisting of about anacardic acid, CzzHazOa, and 10%cardol, C32Hs204, with very small fractional percentages of othermaterials.

Pyrolytic distillation causes conversion into phenols. Our reagents maybe obtained from cashew nutshell liquid, anacardol(3-pentadecadienylphenol), cardanol (dihydroanacardol or3-pentadecenylphenol), and hydrogenated cardanol (dihydrocardanol ortetrahydroanacardol or S-pentm decylphenol) Commercially, these productsap- Dear on the market in one of three forms: cardanol, treated cashewnutshell liquid, and hydrogenated cardanol.

The level of oxyalkylation employed to produce satisfactory reagentswill depend upon a number of factors. In all cases, however, theultimate product must possess surface-activity and must be hydrophile,to come within our invention. Since ethylene oxide possesses thegreatest oxygen-to-carbon ratio of the non-hydroxylated alkylene oxideswhich are usable, it will ordinarii require fewer moles of it to producea required level of surface-activity than it would of butylene oxide,for example. For some purposes, however, it may be desirable to employbutylene oxide rather than ethylene oxide, in spite of the above fact.Sometimes an intermediate product may have a somewhat unsatisfactorysurfaceactivity; but this is immaterial so long as the ultimate product,asserted to come within our invention, has the requiredsurface-activity.

For some purposes, such as clemulsification of petroleum water-in-oilemulsions, the preferred reagent usually has a relatively high degree ofwater-solubility. For other uses, lower levels thereof, probably moreproperly to be termed water-dispersibility or self-emulsifiability, maybe preferable. All our reagents are hydrophile, however; and, as such,all possess either water- 'solubility, water-dispersibility, orself-emulsifiebility in water.

The reagents exhibit great versatility and utility as one goes fromminimum to maximum hydrophile characteristics in them by varying theropertion oi alkylene oxide employed in their preparation. Minimumhydrophile properties may appear, for instance, when about twoethyleneoxy radicals have been introduced for each phenolic hydroxylgroup originally present. Such minimum hydrophile property means thatthe product shows at least seif-dispersibility or selfemulsifiability indistilled water at from 30 to 60 C. in concentrations between 0.5% and5%. Such minimum dispersibilit tests are preferably conducted in absenceof water-insoluble solvents. Such sol r dispersion should be at leastsemistable, i. e., it should persist for from 30 minutes to 2 hourswithout showing appreciable separation. Of course, water-insolublesolvents may be present; and if the mixture of reagent and suchinsoluble solvents is at least semi-stable, then, obviously, thesolvent-free reagent would be even more water-dispersible.

The product may be so slowly dispersible, e. g., because of solid orsemi-solid character, that it is difficult to prepare such dispersion.In such cases, mixing the product with approximately an equal proportionor less of an alcohol like methyl or ethyl alcohol, or with ethyleneglycol diethylether or diethylene glycol diethylether, etc., will resultin the formation of a readily dispersible material. The amount ofsolvent so included in the final aqueous dispersion is insignificant,since the latter is 0.5% to 5% concentrated as to oxyalkylateddiphenylolmethane.

'Mere visual examination of mixtures of the reagent with water maysufllce to indicate surface-activity, i. e., the product produces ahomogeneous mixture which foams or shows emulsifying power. All theseproperties are 'related through adsorption at the interface, forexample, at the gas-liquid or the liquid-liquid interface. If desired,surface-activit may be measured in any of the quantitative methods fordetermining surface and. interfacial tension, such as by mean of aDuNouy tensiometer or a dropping pipett From the standpoint ofsurface-activity, it wi be apparent that the present reagents representa class of materials differing from each other by small increments, asthe oxyalkylating agent an the proportions of oxyalkylating agent arevarieq, Employing different. homologous phenolic react. ants anddifferent homologous aldehydic react. ants, one is enabled to producewith nicetyi product of any desired surface-activity characteristics.

As stated above, among the principal embodiments of our reagents arecertain esteriiled derivatives of the foregoing oxyalkylateddiphenylolmethanes, which themselves constitute another importantembodiment thereof. Since the oxyalkylated diphenylolmethanes possess atleast two alcoholic hydroxyl groups, they are capable of reacting withone moleof an acidic reactant to produce a fractional ester; or with twoor more moles of such acidic reactant to produce total esters. Bothester forms are included within the present invention, so long as theacidic reactants employed meet the following specifications. (Forsimplicity, we are proceeding hereinafter as if the oxyalkylateddiphenylolmethanes were derived from a non-hydroxylated alkylene oxide,and

therefore as if such product possessed only two alcoholic hydroxylgroups. We have already specified that glycide and methylglycide aresuitable oxyalkylatin agents to produce our reagents. We repeatv thatstatement now, to make it plain that in some instances our simpleoxyalkylated diphenylolmethane products may contain four or more ratherthan two alcoholic hydroxyl groups.)

The acidic reactant employed to produce such fractional Or total estermay be any monobasic carboxylic acid, whether saturated or not, whichhas 8 carbon atoms and not more than 32; Included among such acceptableacidic reactants are the higher fatty acids, petroleum acids like thenaphthenic acids and acids produced by the oxidation of petroleum wax,rosin acids like abietic acid, etc. Of all the acceptable acids of thisgeneral class, we prefer to employ the higher fatty acids containingfrom 8 to 32 carbon atoms. We have found the modified higher fatty acidsequivalent to the fatty acids themselves. For example, the chlorinated,brominated, hydrogenated modifications may be substituted for the simpleacids. Other modifications are suitable, so long as they retain thefundamental characteristics of the fatty acids, e. g., are capable offorming alkali salts which are soap-like or detergentlike in character.Instead of the acids, the acyl chlorides or acid anhydrides may beemployed in the esterification reaction, just as may any otherfunctional equivalents of the free acids. For example, low molal estersof such acids, like the methyl or ethyl esters, may beutilized toadvantage in some instances. They are effective by virtue of analcoholysis reaction in which the alkyl group is displaced from theester by the diphenylolmethane residue, with concomitant liberation ofmethyl or ethyl alcohol. The use of such low molal esters is attractive,in that any excess thereof, and also the methyl and ethyl alcoholproduced in such alcoholysis reaction, may be readily removed from thereaction mass by distillation.

If desired, mixed esters of our diphenylolmethanes may be prepared byusing different high molal monocarboxylic' acids in the foregoingesterification step. Furthermore, so long as a high molal monocarboxylicacid is employed to esterify at least one of the alcoholic hydroxylgroups of the diphenylolmethane, monocarboxylie and other obviousequivalents capable of supply ing the acyl radical required in theesteriflcation.

Of the ester forms of reagents, we preferthose 7 prepared from higherfatty acids having 18 carbon atoms, and particularly such higher acidsas are unsaturated. Among such fatty acids are oleic, linoleic,linolenlc, and ricinnleic acids. If desired, the mixed fatty acidsrecovered from the splitting of any selected saponiflable fat or oil,such as cottonseed oil, soyabean oil, corn oil, etc., may be employed asthe esterifying agent. All such high molal monocarboxylic acids aboverecited are members of the class of detergentfcrming acids, becausetheir alkali salts are soaps or soap-like products. Esters ofunsaturated C-18 acids with our oxyalkylated diphenylolmethanes areparticularly desirable where our reagents are to be used as demulsifiersfor resolving petroleum emulsions of the Water-in-oil type.

The ester forms of our reagents are useful as intermediates in furtherreactions, so long as they retain a functional group capable ofparticipating in such reaction. For example, the fractional esters stillcontain one alcoholic hydroxyl group per molecule, which is susceptibleto further esterification. The total esters are likewise often useful infurther reactions. For example, conjugated double bonds in the fattyacid residue are reactive, the alcoholic hydroxyl group of thericinoleic acid residue is reactive, etc.

Having described the reagents of our invention in broad outline, wepropose new to consider certain aspects thereof in greater detail.

Our reagents may be prepared in any desirable manner; but ordinarilythey are prepared in two or three steps. First, the diphenylolmethane isprepared; then it is 'oxyalkylated; and finally derivatives of suchoxyalkylated products, such as the esters, are prepared from them.Manufacture of the parent diphenylolmethane will be first considered. Itusually involves formaldehyde and a phenolic reactant of the kinddescribed in detail above. Condensation reactions of this type are wellknown and do not require detailed description. We might note that iffurfuraldehyde is used as the aldehydic reactant, alkaline condensingagents or catalysts may preferably be employed; otherwise acidiccatalysts are usually preferred. The condensation reactions producediphenylolmethanes which are oily to very viscous semi-solids, or evensolids, in appearance.

In all cases, substantially 2 moles of phenol are combined with 1 moleof aldehydic reactant. The reactant proportions are usually preferablyslightly in excess of 1 mole of aldehyde to 2 moles of phenol, in orderto facilitate completion of the reaction, as mentioned above. Forexample, such ratio may be 1.05 to 2 or 1.1 to 2, or possibly as greatas 1.2 to 2, without departing from our invention. Increasing thealdehyde proportion unduly is to be avoided, because it tends to giveproducts containing more than 2 phenolic nuclei in the molecule.Increasing the phenolic proportion, i. e., reducing the aldehydeproportion unr 10 duly, may result in waste of phenol in that it willremain uncombined with, the aldehyde. Such excess is therefore to beavoided. (It will probably become oxyalkylated, however.)

Note that, for our purpose, the resulting diphenylolmethane need be onlytechnically pure. In other words, if it contains even as little as 65 or70% of the desired diphenylolmethane, the product is frequentlyacceptable. The remainder, a composition not included within ourinvention, is usually inert'rather than positively harmful. Of course,it may needlessly increase the cost of the product to have lesseffective or ineffective byproducts or uncombined materials present. Wenaturally prefer to have the highest quality product obtainable. Excessfree phenol, if volatile, may be recovered by distillation and employedto make later lots of the product, if desired.

Since the phenolic reactant is water-insoluble and frequently solid, andthe preferred aldehydic reactant, formaldehyde, is usually employed asthe commercial aqueous solution of 37-40% concentration, we have foundit most desirable to employ, in addition to heat and vigorous agitation,a minor proportion of a wetting or emulsifying agent to promoteemulsiflcation of the mixture. See U. S. Patent No. 2,330,217, datedSeptember 28, 1943, to Hunn, for examples of such preferred procedure asapplied to the manufacture of resins. The following examples illustrateconvenient procedures for preparing the diphenylolmethanes containingtwo phenolic nuclei, which are the parent substances of our reagents.While our products are distinctly not resins, because the latter havedifferent properties and commonly contain 3 or more, and usually 4 or 5or more phenolic residues, the Hunn procedure noted is applicable here.

/ DIPHENYLOLMETHANE Example 1 Use p-octadecyl phenol, 8'7 grams;formaldehyde (37%), 10.5 grams (molal ratio, 2 to 1); concentratedhydrochloric acid, 1 gram; Nacconal NRSF (a product of National AnilineG0,), 0.2 gram; and xylene, 150 grams. (Add the xylene before theformaldehyde.) The reactants are mixed in a vessel equipped with areflux condenser, stirrer, thermometer, and coils. Heat to about 0.,where a mildexothermic reaction sets in, raising the temperaturesomewhat. Increasing creaminess is noted after 15-30 minutes ofrefluxing; Reflux 1 hour. The xylene is a solvent for subsequentoxyalkylation and is also useful to facilitate removal of water from thereaction mass. Distill the water of solution and of reaction, with thexylene, using a trap arrangement which permits return of the xylene tothe vessel, but removal of water as distilled. The product. whensolvent-free, is clear, reddish, soft, tacky, and xylene-soluble. Itcontains about of our reagent.

DIPHENYLOLM'ETHANE Example 2 Use p-nonylphenol, 220 grams; formaldehyde(37%), 43 grams (molal ratio, 1 to 0.531); concentrated hydrochloricacid, 2 grams; Nacconal NRSF (a product of National Aniline 00.), 0.8gram; and xylene, grams. Proceed as in the preceding example. Theproduct, when solventfree, is clear, reddish, soft-to-fluid, andxylenesoluble.

Drrmnoturrrumr Example 3 Use cardanol, 576 grams; formaldehyde (37%) 81-grams (molal ratio, 2 to 1); concentrated. hydrochloric, acid, 4 grams;Nacconal NBS-F (a product of National Aniline Co.) 1.5 grams. Proceed asin Example 1, except that the xylene is added -ju'st before water isdistilled. The product, when solvent-free, is dark red, soft orsemi-fluid, and xylene-soluble.

and heat the mixture to about 150 C. Introduce the formaldehyde slowly,the temperature grad- .ually receding to about 100-110 C. as waterforms. Reflux the mass for 1 hour, add 100 grams of xylene, and distillthe water, to about 150 C. This is essentially the procedure employed:in U. 8. Patent No. 2,373,058, dated April 3, 1945, to Bilberkraus.

DIPHENYLOLMETHANE Example 5 Use the phenols of Examples 1 to 3, above;but substitute, for formaldehyde, butyraldehyde or hcptaldehyde,respectively.

In general, preparation of the diphenylolmethane may be accomplishedmerely by reacting the phenol and the aldehyde in absence of added inertsolvent. However, if the use to which the final product is to be putdoes not rule out the use of such solvents, they are often employed toadvantage, as shown by the foregoing examples. For example, xylene orhigh-boiling aromatic petroleum solvent may be included in thereactionmass to reduce its viscosity. On completion of the reaction, itfacilitates removal of the water of solution (if the, aldehyde was usedin aqueous solution) and the water of reaction. We prefer to employ suchsolvent at this point in the preparation of such of our reagents as areutimately to'be used as demulsiflers, as above noted, because thefinished demulsifying agent will probably be required to contain aviscosity-reducing solvent anyway, if it is to be used commercially.

Having prepared the parent diphenylolmethane by the foregoing or otherprocedures-details of such preparation being well known and also beingshown in the examples above, 'or the materials having been purchased, ifobt'ainablewe next oxyalkylate the material.

Oxyalkylation of such diphenylolmethanes, as above stated, results inthe interposition of an alkyleneoxy group or multiples thereof betweenthe original phenolic hydroxyl oxygen atom and its companion hydrogenatom; and the conversion of such original phenolic hydroxyl groups intoalcoholic hydroxyl groups. Because such oxyallwlation procedureintroduces oxygen atoms into the -molecule being treated, in the form ofether linkages, it generally confers increasing water-solubility on suchmolecule. Particularly, in such cases, it confers increasingwater-solubility by small increments, so that substantially any desiredlevel of water-solubility, water-dispersibility, or self-emulsifiabilitymay be conferred simply by controlling the number of alhleneoxy groupsso introduced. For different Purposes, it may be desirable to havehigher or lower levels of oxyalkylation.

rmreagents which are eflective as dem'ulsiilers for crude oil emulsicnsof the water-in-oil type. we prefer to employ a relatively high level ofoxyalkylation, and prefer to employ ethylene oxide to achieve it. Inusing ethylene oxide, we have found that in some cases surface-activityand self-emulsiiiabllity begin to appear when there has been added abouthalf as much ethylene oxide as there is diphenylolmethane present, byweight. For some purposes, where hydrophile qualities are desired, butwith low water-solubility, such result might be achieved by usingsmaller proportions of ethylene oxide or by employing some higheralkylene oxide, e. g., butylene oxide, which has a smalleroxygen-to-carbon ratio, and hence confers less water-solubility permolecule added than does ethylene oxide.

Oxyalkylation is a well known procedure. The alkylene oxide is added,either continuously or batchwise, in gaseous or liquid form, to theliquid or molten diphenylolmethane, at a temperature at which thealkylene oxide will be absorbed. While the reaction is an exothermicone, it is usually required to heat the parent diphenylolmethane at thebeginning of the reaction, and sometimes throughout it, to temperaturesgenerally lying between 50 and 250 C. 'R'eaction is preferably effectedin a closed vessel,

capable of withstanding the pressures developed,

to prevent loss of alkylene oxide. Pressures are sometimes low, of theorder of 10 to 20 p. s. 1. gauge; but in some instances; especially inmore exhaustive oxyalkylation, pressures of the order of 100 p. s. i.,or even 1,000 p. s. i., may be encountered. In some instances, thereaction is so vigorous that cooling must be practised, or the stirringrate must be reduced, to reduce eflectiveness of contact and consequentrate of reaction.

Catalysts are preferably employed in this reaction; and alkalinecatalysts are more desirable than acidic catalysts. Caustic soda, alkalicarbonates, alkali alcoholates like sodium methylate, alkali soaps,etc., may be so used. The amounts employed usually lie between 0.2 and2% by weight of the diphenylolmethane.

In all instances the proportion of alkylene oxide 'hydroxyl groupspresent (the first such unit added to each original phenolic hydroxylgroup transforming it into an alcoholic hydroxyl group).

If the oxyalkylated diphenylolmethane is to be used as an intermediatein the preparation of a fractional or total ester, the influence of theesterifying acid on the surface-activity of the resulting ester must beconsidered. For instance,

if one employs an oxyalkylated diphenylolme ane which is itself onlymarginally surface-active, and esterifies it with a monocarboxylic acidhaving, for example, 18 carbon atoms, it is possible that the effect ofsuch esterifying acid will be such as to remove the resulting ester fromthe class of reagents acceptable in our invention, because such estermay exhibit negligible surfaceactivity. In another case, theintermediate oxyalkylated diphenylolmethane employed in such 13esteriflcation may show undesirably high and almost truewater-solubility; but the eflect oi the high molal esterifying acidwould tend to reduce the water-solubility; and the resulting ester mightshow more desirable surface-activity for that purpose.

One method of varyingthe oxyalkylation level is to add a smallproportion of alkylene oxide, substantially sumcient to convert only oneof the two alcoholic hydroxy] groups to an alcoholic hydroxyl group;than to esterify this alcoholic group with the desired high molal acid;and then to revert to oxyalxylation to introduce sufficient allryleneoxide to solubilize the fractional ester to the desired level.

Surface-activity of the reagents of our invention is determinablequantitatively by finding the surfaceor interfacial tension of diluteaqueous dispersions, e. g., by means of a DuNouy tensiometer or droppingpipette, etc. A value considerably lower than that of the solution watershould be found in dilutions of 1% and less, if the dissolved substanceis surface-active. If it were truly dissolved in the water, the valueswould approximate that of water. Unless the reagent has been solubilizedat least to the extent that a dilute aqueous dispersion, e. g., of 0.5%to concentration, exhibits substantial homogeneity for periods of from30 minutes to 2 hours, it is usually not possible to make a satisfactorymeasurement of its surfaceor interfacial tension. The acceptability of areagent in our invention is determined by the fact that it has at leastsufllcient surface-activity to produce an aqueous dispersion of 0.5% to5% concentration which is substantially stable or at least semi-stablefor 30 minutes to 2 hours. At the lower limit of acceptability,therefore, it may be impracticable to make a quantitative measurement ofsuch surface-activity, as just noted. In the present instance, We applythe word hydrophile to mean products which exhibit at least such minimumsurface-activity as shown by the fact that they are capable ofproducing, with water, dispersions which are at least of such minimumstability. insufficiently solubilized reagents are consequently excludedfrom the scope of our invention.

As examples of methods for preparing oxyalkylated diphenylolmethanes ofthe present class, we submit the following:

OXYALKYLATED DIPHENYLOLMETHANE Example 1 One gram-mole of thexylene-free product of Example 1, above, (at least 85% pure), is mixedwith 100 grams of xylene and 6 grams of sodium methylate. Ethylene oxideis added in IOU-gram portions. The first portion is quite readilyabsorbed; but subsequent portions are more slowly absorbed. Thediphenylolmethane solution should be heated to about 80 C. beforeintroducing the ethylene oxide, although the reaction increases thetemperature to as much as 150 C. or more. The product, after the firstlot of ethylene oxide has been absorbed, shows only slightwater-dispersibility in the presence of the added xylene; butwater-dispersibility improves regularly with addition of ethylene oxide,until it is quite acceptable after about three IUD-gram portions havebeen absorbed. A total of 5 nortions were employed; but more may beused, if desired. Also, the ethylene oxide may be introducedcontinuously instead of intermittently if facilities permit.

OxYALxYtArzn Drrnnxrtotuzrnllnn Example 2 Substitute the products ofExamples 2 and 3, diphenylolmethane, above, in the foregoing procedure.

Oxnrxrmrsn DIPHENYLOLMETHANE Example 3 1 Substitute propylene oxide orbutylene oxide 1 for ethylene oxide in Examples 1 and 2, imme-- diatelyabove.

As previously stated, one of the preferred embodiments of our reagentsis the ester, both fractional and total, with high molal monocarboxylicacids. Such esteriflcation is commonly conducted, using the free highmolal acid, with small proportions of conventional esteriflcation catailysts, e. g., aromatic sulfonic acids, alkylated aromatic sulionicacids, alkyl phosphoric acids, hydrogen chloride gas, etc. and heatingto temperatures somewhat above 100 C. Completeness of the reaction maybe followed in such cases by noting the amount of water ofreaction whichis distillable; or it may be followed by determining the reduction infree carboxyl group.v For fractional esters, of course, the proportionof esterifying acid must be limited to the molal proportion required toesterif only a part of the alcoholic hydroxyl groups present. It hasalready been stated that functional equivalents of the free high molalacids may be employed in this esterification reaction.

FRACTIONAL HIGH MOLAL Es'rnn or OXYALKYLA'I'ED DIPHENYLOLMETHANE Example1 One mole of the oxyalkylated diphenylolmethane produced inOxyalkylated diphenylolmethane, Examples 1 to 3, above, (at least pure)is reacted with an equi-molar proportion (282 parts) of oleic acid, inxylene solution. After refluxing 1 hour, the vessel containing themixture is fitted with a side-arm trap and is heated to distill theapproximately 18 parts of water produced in the esterification.

FRACTIONAL HIGH MOLAL Es'rxa or OXYALKYLATED DIPHENYLOLMETHANE Ewample 2Repeat Example 1, immediately above, except use 298 parts of rlcinoleicacid as the esterifying acid.

FRACTIONAL HIGH MOLAL Esrnx or OXYALKYLATED DIPHENYLOLMETHANE Example 3Repeat Examples 1 and 2, immediately above, except use 280 parts oflinoleic acid or 278 parts of linoleni acid as the esterifying acid;

I FRACTIONAL HIGH MOLAL ESTER OF OXYALKYLATED DIPHENYLOLMETHAN'E Example4 FRACTIONAL HIGH MOLAL Es'rna or OXYALKYLATED DIPHENYLOLMETHANE Example5 Repeat Examples 1 to 4, immediately above,

accuse;

except use approximately 280 parts of soyabean fatty acids as theesterifying acid.

When one employs twice as many moles of high molal esterifying acid asof oxyalkylated diphenylolmethane (assuming non-hydroxyiated alkyleneoxides were used) in the above esteriiication procedure, total estersare formed. Such total esteriilcation reactions are even easier toconduct than those employed to produce fractional esters, because thepresence of excess esterifying acid is not important. It may be removedat the end of the reaction, or it may be allowed to remain in the mass,if its presence is not undesirable in the projected use of the totalester. Employment of the methyl or ethyl ester of the esterifying acidis quite practicable here. The free acids, their acyl chlorides, theiranhydrides, etc., may be equally well employed as in the case of thepreparation of the fractional esters above.

Tour. HIGH MDLAL Es'rna or OxYALKYLArEp DIPHENYLOLMETHANE Example 1 nmore times as much high molal acid as in the preceding examples would berequired to produce total esters from oxyalkylated diphenylolmethanesprepared from glycide or methylglycide.)

Tor/u. HIGH MOLAL Esme or OXYALKYLATED DIPHENYLOLMETHANE Example 2Repeat Example Limmediately above, except use an equivalent amount ofthe respective acyl chloride instead of the free fatty acid in eachcase. Note that hydrogen chloride, not water, will be the other productof the esterification reaction here.

So long as one of the alcoholic hydroxyl groups of the oxyalkylateddiphenylolmethane has been esterified with a high molal monocarboxylicacid, as above illustrated, the remaining such hydroxyl group or groupsmay be esterified with a low molal monocarboxylic acid, containing 7carbon atoms or less, to produce a mixed ester. The following examplesembody this phase of our reagents.

MIxnn Es'rsn or OXYALKYLATED DIPHENYLOLMETHANE Example 1 The fractionalesters produced in Fractional high molal ester of oxyalkylateddiphenylolmethane, Examples 1 to 5, above, are heated with proportionsof either acetic acid, hydroxyacetic acid, lactic acid, or butyric acid,sufll cient to esterii'y the remaining free alcoholic hydroxyl groupspresent in such fractional esters. An equivalent amount of water ofesterification is group of the oxyalkyiated diphenylolmethane and thenon-hydroxylated acids carboxyl group.

For example, if ricinoleic acid and a low molal non-hydroxylated acidare to be esterified, the ricinoleic acid is preferably reacted last.

In the foregoing discussion, no consideration has been given thethrought that symmetrical and unsymmetrical forms of oxyalkylateddiphenylolmethanes may be prepared. For example, minimum oxyalkylationmay be conducted, so as to introduce a total of two moles of alkyleneoxide, which convert the two phenolic hydroxyl groups to alcoholichydroxyl groups. Then, one of the alcoholic hydroxyl groups may beblocked by reacting the partially oxyalkylated product with an acid, e.g., a high molal monocarboxylic acid, to produce a fractional ester.Such fractional ester may then be oxyalkylated further, all of theadditional alkylene oxide being added at the other or free alcoholichydroxyl group. In such case, the esterified hydroxyl group positionwould possess only one alkylene oxide residue; all others introducedwould be located at the other alcoholic hydroxyl group position.

If desired, this same procedure may be applied, but more alkylene oxideintroduced in the first oxyalkylation step. In such instance, bothalcoholic hydroxyl groups would receive a number of alkylene oxideresidues. Esterification at one of such two positions would then preventany further addition of alkylene oxide there; and any furtheroxyalkylation must .consequently take place at the other position. Thislatter position would then have more alkylene oxide residues than thefirst and esterified position: and the product would likewise beunsymmetrical.

Where all oxyalkylation takes place before any esterification, in asingle preliminary operation, distribution of alkylene oxide residuesbetween the alcoholic hydroxyl positions will be uniform ii the twophenolic nuclei are identical; and symmetrical oxyalkylated esters willresult on subsequent esteriflcation.

Materials of the kind herein disclosed are useful in many arts. They maybe used as wetting, detergent and leveling agents in the laundry,textileand dyeing industries; as wetting agents and detergents in theacid-washing of fruit and in the acid-washing of building stone andbrick; as a wetting agent and spreader in the application of asphalt inroad building and the like; as a constituent of soldering fluxpreparations; as a flotation agent in the flotation separation of 5various minerals; for flocculating and coagulatdistilled oil, aftersuitable refluxing; and mixed esters of said oxyalkylateddiphenylolmethanes are the resulting product.

If a total ester containing the residue of a hydroxylated monocarboxylicacid is desired, it is preferable to produce the fractional ester of anynon-hydroxylated acid employed; and to use the latter in the secondesterification step. This avoids any possibility of reaction between thehydroxyl group of the hydroxylated acid and the carboxyl group of theother acid, in preference to ing negatively-charged particles fromvarious aqueous suspensions such as sewage, coal-washing waste water,various trade wastes, and the like; as germicides and insecticides; asemulsifiers for cosmetics, spray oils, water-repellent textile finishes,etc. The aforementioned uses are by no means exhaustive as to industrialuses. The most important use of our new composition of matter is as ademulsifler for dehydrating waterin-oil emulsions, and more specificallyemulsions of water or brine in crude petroleum.

The chemical reagents herein described are also particularly desirablefor use as break inducers in the doctor treating procedure forsweetening gasoline. (See U. 8. Patent No. 2,157,223, dated May 9, 1939,to Sutton.)

Chemical compounds of the kind herein described are also of value assurface tension depressants in the acldization of .calcareous oilbearingstrata by means of strong mineral acid.

free alcoholic hydroxyllike hydrochloric acid. As to this use, see '0.8. Patent No. 2,233,383, dated February 24, 1941, to De Groote andKaiser. Similarly, some members are effective as surface tensiondepressants or wetting agents in the working of depleted oilbearingstrata by flooding, in secondary recovery operations. As to this lastnamed use, see U. S. Patent No. 2,226,119, dated December 24, 1940, toDe Groote and Keiser.

We have prepared a number of representative oxyallrylateddiphenylolmethanes and esters thereof, as described herein. We havetested such representative oxyallrylated diphenylolmethane products andtheir esters, as herein described, and have found them to be eflectivedemulsifiers for oil-field emulsions oi the water-inoil type. We haveadditionally determined that such cxyalkylated products and their estersare valuable for purposes where surface-active agents are conventionallyemployed. We have also determined that the oayallrylated products andtheir esters herein described can be used as intermediates for themanufacture of more complicated derivatives.

While the examples show a number of representative usable phenols, itmay be well to do scribe our preferred tri-iunctional phenolic reactantshere. These are prepared from the phenolic compositions present in orderived irom the oils extracted from the anacardium genus ofanacardiaceae family. Cashew nutshell liquid is described as consistingoi about 90% anacardic acid, C22'H3203, and 10% cardol, (l'aaHeoUi, Withvery small fractional percentages of other materials.

Pyrolytic distillation causes conversion into phenols. Our reagents maybe obtained from treated cashew nutshell liquid, anacardoi (3-pentadecadienylphenol), cardanol (dihydroana cardol or3-pentadecenylphenol), and hydrogenated cardanol (dihydrocardanol ortetrahydroanacardol or 3-pentadecylphenol). Commercially, these productsappear on the market in one of three forms: cardanol, treated cashewnutshell liquid, and hydrogenated cardanol.

its an example of diphenylolmethane prepared from one suchtri-functional phenol, and suitable for subsequent oxyalhylation, thefollowing directions may be given: Use cardanol, '76 grains;formaldehyde (37%), 61 grams (molal ratio, 2 to 1) concentratedhydrochloric acid, 1 grams; Nacconal NRSF (a product of National Aniline130.), 1.5 grams. This product, as is well known, is a monoalkyl(Clo-C20, principally benzene monosulionic acid sodium salt. Proceed asin Example 1 Diphenylolmethane, above, except that the xylene is addedjust before water is distilled. The product, when solvent-tree, is darkred, soft or semi-fluid and xylene-soluble.

Attention is directed to the fact that the present application is one ora series, Serial Nos. 751,600, 751,601, 751,602, 751,603, 751,604,7516M, 751,615, 751,616, 751,613, 751,621, 751,622, 751,625, 751,626,751,627 and 751,628, all filled 01 even date, and all relating tokindred subjectrnatter. Application Nos. 751,611,, 751,615, 751,616,751,618, 751,621 and 751,622 are now abancloned.

Having thus described our invention, what we claim as new and desire tosecure by Intters Patent is:

1. A surface-active oxyalkylated derivative or a diphenylolmethanehaving the formula wherein one occurrence of R2 represents hydrogen andthe other occurrence represents a member of the class consisting ofhydrogen and organic radicals containing 7 carbon atoms or less; Rt is amember of the class consisting of alkylene radicals and hydroxyalkyleneradicals and contains a carbon atoms or less; R0 is a monocyclicphenolic nucleus orilio-linked to the carbon atom C; R5 is a hydrocarbonradical containing from 0 to 24 carbon atoms and substituted in the paraposition of the phenolic nucleus Re; R1 is a member of the classconsisting of hydrogen, acyl radicals of monocarboxylic acids containingfrom 8 to 32 carbon atoms, and acyl radicals of monocarboxylic acidscontaining from 1 to 32 carbonatoms, with the proviso that if eitheroccurrence of R7 represents an acyl radical, at least one suchoccurrence must represent the acyl radical of a monocarboxylic acidhaving from 8 to 32 carbon atoms; and n is a number between 1 and andwith the final proviso that said derivative, in absence ofwaterinsoluble solvents, is surface-active to the extent that it iscapable of forming at least a semistable aqueous dispersion in 0.5% to5% concentration, said surface-activity being due to onyallrylation inthe phenolic hydroxyl position.

2. lhe product of claim 1, wherein one occurrence of R3 representshydrogen, and the other occurrence of R2 represents an aliphaticradical.

3. The product of claim 1, wherein both occurrences of Ra representhydrogen.

a. The product of claim 1, wherein both occurrences of Ra representhydrogen, and R1 is the ethylene radical CsHt.

5. The product of claim 1, wherein both occurrences of Ra representhydrogen; R1 is the ethylene radical C2111; and both occurrences of nrepresent the same number.

6. The product of claim 1, wherein one occurrence of R1 representshydrogen, and the other occurrence of R7 represents the acyl radical ofa monocarboxylic acid containing from 8 to 32 carbon atoms.

7. The product of claim 1, wherein one occurrence of R2 representshydrogen; the other occurrence of R2 represents an aliphatic radical;one occurrence of R1 represents hydrogen; and the other occurrence of R1represents the acyl radical of a monocarboxylic acid containing from 8to 32 carbon atoms.

8. The product of claim 1, wherein both occurrences of R2 representhydrogen; one occurrence of R1 represents hydrogen; and the otheroccurrence of R7 represents the acyl radical of a monocarboxylic acidcontaining from B to 32 carbon atoms.

9. The product of claim 1, wherein both occurrences of R2 representhydrogen; R4 represents the ethylene radical Cal-1i; one occurrence ofR7 represents hydrogen; and the other occurrence of R1 represents theacyl radical of a monocarboxylic acid containing from 8 to 32 carbonatoms.

10. The product of claim 1, wherein both occurrences of R2 representhydrogen; R4 represents the ethylene radical CsHi; one occurrence of R1represents hydrogen; the other occurrence of R1 represents the acylradical of a mono- 19 carboxylic acid containing from 8 to 32 carbonatoms; and both occurrences of 11. represent the same number.

11. The product of claim 1, wherein one occurrence of R1 represents theacyl radical of a monocarboxylic acid containing from 8 to 32 carbonatoms, and the other occurrence of R1 represents the acyl radical of amonocarboxylic acid containing from 1 to 32 carbon ato 12. The productof claim 1, wherein one occurrence of R2 represents hydrogen; the otheroccurrence of R2 represents an aliphatic radical; one occurrence of R1represents the acyl radical of a monocarboxylic acid containing from 8to 32 carbon atoms; and the other occurrence of R7 represents the acylradical of a monocarboxylic acid containing from 1 to 32 carbon atoms.

13. The product of claim 1, wherein both occurrences of R2 representhydrogen; one occurrence of R7 represents the acyl radical of amonocarboxylic acid containing from 8 to 32 carbon atoms; and the otheroccurrence of R1 represents the acyl radical of a monocarboxylic acidcontaining from 1 to 32 carbon atoms.

14. The product of claim 1, wherein both occurrences of R2 representhydrogen; R4 represents the ethylene radical C2114; one occurrence. ofR7 represents the acyl radical of a monocarboxylic acid containing from8 to 32 carbon atoms; and the other occurrence of R1 represents the acylradical of'a monocarboxylic acid containing from 1 to 32 carbon atoms.

15. Theproduct 01' claim 1, wherein both occurrences of R: representhydrogen; R4 is the ethylene radical can; one occurrence of R1represents the acyl radical of a monocarboxylic acid containing from 8to 32 carbon atoms; the other occurrence of R1 represents the acylradical of a monocarboxylic acid containing from 1 to 32 carbon atoms;and both occurrences of n represent the same number.

16. The product of claim 15, wherein m represents the residue derivedfrom nonylphenol.

17. The product of claim 15, wherein RsRe represents the residue derivedfrom dodecylphenol.

18. The product of claim 15, wherein RsRa represents the residue derivedfrom octadecylphenol.

MELVIN DE GROO'I'E. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS De Groote Oct. 2, 1945

1. A SURFACE-ACTIVE OXYALKYLATED DERIVATIVE OF A DIPHENYLOLMETHANEHAVING THE FORMULA.